||||||||| USOO5514437A United States Patent (19) 11 Patent Number: 5,514,437 Tanner et al. (45) Date of Patent: May 7, 1996

(54) ARTIFICIALTANNING COMPOSITIONS 2nd edition, Dec. 10, 1973, vol. 1, pp. 293–305 Wiley-Inter HAVING IMPROVED STABILITY Science, New York. Merck German Technical Data sheet, Nov. 24, 1993. (75) Inventors: Paul R. Tanner, Maineville; Larry R. Kawashima et al., "Nonenzymatic Browning Reactions of Robinson, Lebanon, both of Ohio Dihydroxyacetone with Amino Acide or Their Esters', Agric. Biol. Chem., 44(7), 1595–1599 (1980). (73) Assignee: The Procter & Gamble Company, Ingredient label from packaging, Bain de Soleil Tanning Cincinnati, Ohio Creme, copyright 1993. A. Meybeck, "A Spectroscopic Study of the Reaction Prod 21 Appl. No.: 219,053 ucts of Dihydroxyacetone with Amine Acids”. J. Soc. Cos 22 Filed: Mar. 29, 1994 met. Chem, 28, 25-35 (1977). E. Wittgenstein et al., “Reaction of Dihydroxyacetone (51) Int. CI.' ...... A6K7/02 (DHA) with Human Skin Callus and Amino Compounds', J. 152 U.S. Cl...... 424/63; 424/59; 424/60 Invest. Derm, 23, 283-286 (1961). 58) Field of Search ...... 424/63, 60,59 M. F. Bobin et al., “Effects of Color Adjuvants on the Tanning Effect of Dihydroxyacetone', J. Soc. Cosmet. 56) References Cited Chem., 35, 265,272 (Aug. 1984). U.S. PATENT DOCUMENTS Ingredient label from Elizabeth Arden's Spa for the Sun Self Tanner SPF 15 Product, no copyright date available. 2,274,725 3/1942 Meeker et al...... 424/59 2,949,403 8/1960 Andreadis. The Merck Index, Tenth Edition, 1983, Entry 8476. 3,177,120 4/1965 Black et al...... 424/59 V. R. Usdin, “Artificial Tanning Preparations',Cosmetics 3,184,388 5/1965 Kalopissis. ... 424/59 and Toiletries, vol. 91, Mar. 1976 pp. 29–32. 3,272,713 9/1966 Runge ...... 424/59 J. Buchter et al., “The Reaction of Dihydroxyacetone with 3,920,808 11/1975 Fusaro ...... 424/59 Proteins', American Perfumer, Dec. 1960, pp. 46-48. 4,145,413 3/1979 Usdin et al. ... 424/63 N. Kanas et al., "Factors Influencing the Tanning Effect of 4,293,543 10/1981 Cotte et al. . ... 424/59 4,419,343 12/1983 Pauly ...... 424/59 Dihydroxyacetone of the Skin' American Perfumer, Nov. 4,434,154 2/1984 McShane ...... 424/60 1960, pp. 33–34. 4,831,943 5/1989 Grollier et al. . ... 424/59 M. Fleming et al., "Chemistry of Browning Reaction', The 4,847,267 7/1989 Deckner et al. ... 514/311 Sugar Journal, Apr. 1971, pp. 21-27. 5,100,660 37992 Hawe et al...... 424/78.35 K. Laden et al., "The Reaction of o-Hydroxymethyl 5,221,530 6/1993 Janchitraponveget al...... 424f70 Ketones with Skin and Amino Acids, J. Soc. Cosmetic 5,232,688 8/1993 Ziegler et al...... 424/59 Chemists, 16, 777-782 (1965). 5,302,378 4/1994 Crotty et al...... 424/59 Primary Examiner-Shelley A. Dodson FOREIGN PATENT DOCUMENTS Attorney, Agent, or Firm--Anthony D. Sabatelli; David K. 90/61950 5/1991 Australia ...... A61K 7/02 Dabbiere CA72(20):103635B/1969 Czechoslovakia. 227012 7/1987 European Pat. Off...... A61K 7700 57 ABSTRACT 456545 4/1991 European Pat. Off...... A61K 7/42 547864 6/1993 European Pat. Off...... A61K 7/42 The present invention relates to artificial tanning composi 622070A1 11/1994 European Pat. Off...... A61K 7/42 tions having improved stability. These compositions com 34227937 8/1994 Japan ...... A61K 7/42 prise dihydroxyacetone, a salt selected from the group 98(16):132150g 10/1982 Spain ...... A61K 62A4 consisting of metabisulfite salts, sulfite salts, hydrogen 83-825600/47 1/1983 U.S.S.R...... A61K 7/OO sulfite salts, and mixtures thereof. These compositions are WO92/1759 10/1992 WIPO ...... A61KT42 useful for imparting an artificial tanto human skin. In further WO93,092.15 5/1993 WIPO ...... C11D 3/04 embodiments, these compositions also comprise a sunscreen OTHER PUBLICATIONS agent and are also useful for providing protection from the harmful effects of ultraviolet radiation, Technical Bulletin-Salcare SC 92 for Cosmetic/Personal Care applications, Allied Colloids, Suffolk, VA-Undated. M. S. Balsam et al., (ed.) Cosmetic Science and Technology 19 Claims, No Drawings 5,514,437 1. 2 ARTEFICAL TANNING COMPOSITIONS human skin by its reaction with the nitrogen containing HAVING MPROVED STABILITY proteins of the skin. See L. Goldman et al., “Investigative Studies with the Skin Coloring Agents Dihydroxyacetone The present invention relates to compositions useful for and Glyoxal', The Journal of Investigative Dermatology, providing an artificial tan to human skin. These composi 5 vol. 35, pp. 161-164 (1960); E. Wittgenstein et al., “Reac tions exhibit improved chemical and physical stability. tion of Dihydroxyacetone (DHA) with Human Skin Callus These compositions comprise dihydroxyacetone, a salt and Amino Compounds', The Journal of Investigative Der selected from the group consisting of metabisulfite salts, matology, vol. 36, pp. 283–286 (1961); and A. Meybeck, "A sulfite salts, and hydrogen sulfite salts, and mixtures thereof, Spectroscopic Study of the Reaction Products of Dihdyroxy and a topical carrier. In further embodiments these compo 10 acetone With Amino Acids', J. Soc. Cosmet. Chem, 25-35 sitions also comprise a sunscreen agent and are useful for (1977); all of which are incorporated by reference herein in protecting the skin from the harmful effects of ultraviolet their entirety. This incompatibility of dihydroxyacetone with radiation. nitrogen containing compounds has limited the formulation scope of artificial tanning products in the past. 15 Conventional stablilizing agents and antioxidants such as BACKGROUND OF THE INVENTION BHA, BHT, and vitamin E are ineffective for stabilizing A sun-tanned appearance is a symbol of a healthy, artificial tanning compositions containing dihydroxyac dynamic, and active life. Yet, the damaging effects of etone. Surprisingly, it is found in the present invention that sunlight and other sources of ultraviolet radiation on the skin certain salts such as metabisulfite salts, sulfite salts, and are well documented. These effects are cumulative and 20 hydrogen sulfite salts greatly enhance the stability of artifi potentially serious, and include sunburn, skin cancer, and cial tanning compositions containing dihydroxyacetone. The premature aging of the skin. These effects associated with use of metabisulfite salts as anti-oxidants is known in the exposure to ultraviolet radiation are more fully discussed in pharmaceutical area, however, their use has typically been DeSimone, "Sunscreen and Suntan Products', Handbook of limited to extremely low levels, e.g. 0.005%. In the present Nonprescription Drugs, 7th Ed., Chapter 26, pp. 499-511 25 invention, it is found that much higher levels of salts such as (American Pharmaceutical Association, Washington, D.C; metabisulfite, sulfite, and hydrogen sulfite salts, i.e. levels in 1982); Grove and Forbes, "A Method for Evaluating the the range from about 0.025% to about 5%, provide an Photoprotection Action of Sunscreen Agents Against UV-A unexpected enhancement of stability. This enhanced stabil Radiation', International Journal of Cosmetic Science, 4, ity translates into benefits such as increased product shelf pp. 15-24 (1982); and U.S. Pat. No. 4,387,089, DePolo, 30 life, good product performance, maintenance of the aesthetic issued Jun. 7, 1983, the disclosures of all of which are characteristics of the product, i.e. less discoloration and incorporated herein by reference in their entirety. off-odors, and better user acceptance. Sunscreens are the most common agents used for Sun It is therefore an object of the present invention to provide protection. However, sunscreens also have the disadvantage artificial tanning compositions useful for imparting an arti of preventing or greatly diminishing the cosmetically desir 35 ficial tan to human skin, able tanning response. Thus, if an individual uses a sun It is another object of the present invention to provide screen for protection from ultraviolet radiation, he or she artificial tanning compositions which exhibit improved does so at the expense of foregoing a tanned appearance. chemical and physical stability. Furthermore, even if an individual is willing to accept the 40 It is another object of the present invention to provide risks associated with exposure to ultraviolet radiation to artificial tanning compositions which have good color devel obtain a tan, there are situations in which it may not be opment characteristics such as providing a natural looking practical or even possible to do so because of time con and rapidly developing tan. straints, weather conditions, etc. Therefore, it would be It is another object of the present invention to provide highly desirable to develop products for providing a tanned 45 artificial tanning compositions useful for both providing an appearance to the skin, whenever desired without the need artificial tan to human skin and for protecting human skin for exposure to ultraviolet radiation. from the harmful effects of ultraviolet radiation. It is generally known that dihydroxyacetone, when It is another object of the present invention to provide a applied topically to human skin, will produce a tanned method for artificially tanning human skin. appearance, i.e. an artificial tan. U.S. Pat. No. 4,708,865, to 50 Turner, issued Nov. 24, 1987 describes the use of hydro It is another object of the present invention to provide a alcoholic solutions of dihydroxyacetone for tanning the skin; method for artificially tanning human skin and for providing U.S. Pat. No. 4,466,805, to Welters, issued Aug. 21, 1984 protection from the harmful effects of ultraviolet radiation. describes hair and skin coloring formulations containing These and other objects of this invention will become dihydroxyacetone; and U.S. Pat. No. 2,949,403, to Andrea 55 apparent in light of the following disclosure. dis et al., issued Aug. 16, 1960 describes artificial tanning formulations containing dihydroxyacetone in an oleaginous SUMMARY OF THE INVENTION base. The present invention relates to an artificial tanning Dihydroxyacetone is relatively sensitive to heat, light, and composition having improved stability comprising: moisture. It is known that products containing dihydroxy 60 acetone generally have a short shelf life, tending to darken (a) from about 0.1% to about 20% dihydroxyacetone, and develop disagreeable off-odors over time, with a con (b) from about 0.025% to about 5% of a salt selected from comitant loss of product performance. Dihydroxyacetone the group consisting of metabisulfite salts, sulfite salts, can react with other ingredients in a formulation, especially hydrogen sulfite salts, and mixtures thereof, and with nitrogen-containing compounds, such as amines, amino 65 (c) a topical carrier. acids, and the like. In fact, without being limited by theory, All percentages and ratios used herein are by weight of the dihydroxyacetone is believed to provide an artificial tan to total composition and all measurements made are at 25 C., 5,514,437 3 4 unless otherwise designated. The invention hereof can com The scientific literature suggests that the reaction of prise, consist of, or consist essentially of, the essential as dihydroxyacetone with the skin is similar to the Maillard well as optional ingredients and components described Reaction. In this reaction, reducing sugars react with amino herein. acids, proteins, and peptides to form various adducts which are ultimately converted into brown-colored compounds. DETAILED DESCRIPTION OF THE See V. R. Usdin, Artificial Tanning Preparations, Cosmetics INVENTION and Toiletries, vol. 91 pp. 29-32 (March 1976), this refer The compositions of the present invention are useful for ence being incorporated herein by reference in its entirety. providing an artificial tan to human skin. It is found that Without being limited by theory, it is believed that dihy these compositions have improved chemical and physical 10 droxyacetone reacts with the amino acids and amino groups stability and provide improved product integrity. These of the skin keratin thereby forming the brown colored products also have good performance. compounds which provide an artificial tan. It is believed that The term "chemical stability', as used herein, means that the process takes place in the outer layers of the epidermis the various chemical components of the compositions, espe and that the monomer form is responsible for this phenom cially the dihydroxyacetone, do not exhibit appreciable 15 CEO. breakdown or degradation. For example, the compositions Metabisulfite, Sulfite, and Hydrogen Sulfite Stabilizing Salts of the present invention typically retain about 80% or more The compositions of the present invention comprise from of the initially added dihydroxyacetone over about a three about 0.025% to about 5%, preferably from about 0.05% to month period of time at room temperature. The term "physi about 5%, more preferably from about 0.05% to about 1%, cal stability', as used herein, means that the overall com 20 even more preferably from about 0.1% to about 1%, and position exhibits physical characteristics such as resistance most preferably about 0.25% of a stabilizing, antioxidant to developing off-odors and resistance to discoloration and salt selected from the group consisting of metabisulfite salts, darkening. The term is further used herein to refer to sulfite salts, hydrogen sulfite salts, and mixtures thereof. maintenance of viscosity, resistance to syneresis, and in the A metabisulfite salt contains the metabisulfite anion (also case of emulsions, resistance to phase separation. For 25 known as the pyrosulfite anion) which corresponds to the example, the compositions of the present invention typically chemical formula (SOs)'. A sulfite salt contains the sulfite maintain their physical stability for at least about a three anion which corresponds to the chemical formula (SO)'. A month period of time at room temperature. The terms hydrogen sulfite salt contains the hydrogen sulfite anion "chemical stability” and "physical stability” have been sepa (also known as the bisulfite anion) which corresponds to the rately defined herein for convenience. Nevertheless, it is 30 chemical formula (HSO). These salts also contain a cation realized that these two types of stability phenomena are not and can be represented by the general chemical formula XP necessarily distinct and that chemical stability can impact "(SOs)” for metabisulfite salts, XP (SO) for sulfite physical stability and vice versa. salts, and XPCHSO), for hydrogen sulfite salts wherein The term "topical application', as used herein, means to X corresponds to the cation, and m and n are integer values 35 (i.e. 1, 2, 3, 4, etc.) representing the relative ratio of cations apply or spread the artificial tanning compositions to or onto to anions in the salt, and pH represents the value of the the surface of the skin. positive charge on the cation (i.e. +, +2, +3, +4, etc.). It is The term "pharmaceutically-acceptable', as used herein, well known to a chemist of ordinary skill in the art that in means that the compositions or components hereof so the general chemical formulas depicted for these salts, the described are suitable for use in contact with human tissue 40 values form and n are such that the overall charge on the salt without undue toxicity, incompatibility, instability, irritation, is neutral. For example, sodium metabisulfite can be repre allergic response, and the like. sented by the chemical formula Na2SOs, wherein two Dihydroxyacetone sodium cations (each having a +1 charge) are present for The compositions of the present invention comprise from each metabisulfite anion (having a -2 charge). Sodium about 0.1% to about 20%, more preferably from about 2% 45 sulfite can be represented by the chemical formula Na2SO, to about 7%, and most preferably from about 3% to about wherein two sodium cations (each having a +1 charge) are 6% of dihydroxyacetone. present for each sulfite anion (having a -2 charge). Sodium Dihydroxyacetone, which is also known as DHA or hydrogen sulfite can be represented by the chemical formula 1,3-dihydroxy-2-propanone, is a white to off-white, crystal NaHSO, wherein one sodium cation (having a +1 charge) line powder. This material can be represented by the chemi 50 is present for each hydrogen sulfite anion (having a -1 cal formula CHO, and the following chemical structure. charge). Calcium metabisulfite can be represented by the chemical formula CaSOs wherein one calcium cation (hav ing a +2 charge) is present for each metabisulfite anion HOH2C-C-CH2OH (having a -2 charge). Aluminum metabisulfite can be rep 55 resented by the chemical formula Al(SO4) wherein two Dihydroxyacetone can exist as a mixture of monomers aluminum cations (each having a +3 charge) are present for and dimers, with the dimers predominating in the solid each three metabisulfite anions (each having a -2 charge). crystalline state. Upon heating or melting, the dimers break See also The Merck Index, Tenth Edition, (1983), Sodium down to yield the monomers. This conversion of the dimeric Metabisulfite, Entry 8476, p. 1237, Sodium Sulfite, Entry form to the monomeric form also occurs in aqueous solution. 60 8528, p. 1242, and Sodium Bisulfite, Entry 8419, p. 1231, all See The Merck Index, Tenth Edition, entry 3167, p. 463 of which are incorporated by reference herein in their (1983), and "Dihydroxyacetone for Cosmetics', E. Merck entirety. Technical Bulletin, 03-304 110, 319 897, 180588; both of Metabisulfite, sulfite, and hydrogen sulfite salts useful these references being incorporated herein by reference in herein include those selected from the group consisting of their entirety. Dihydroxyacetone is commercially available 65 alkali metal salts (for example lithium, sodium, potassium, from E. Merck (Darmstadt, Germany) and Gist-Brocades and the like), alkaline metal salts (for example beryllium, Food Ingredients, Inc. (King of Prussia, Pa.). magnesium, calcium, and the like), ammonium salts, and 5,514,437 S 6 mixtures thereof. The ammonium salts are defined herein to (March 1987); U.S. Pat. No. 4,960,764 to Figueroa et al., encompass those salts containing both the unsubstituted issued Oct. 2, 1990; and U.S. Pat. No. 4,254,105 to Fukuda ammonium cation (i.e. NH) as well as various substituted et al., issued Mar. 3, 1981. ammonium cations. Nonlimiting examples of substituted The topical carrier can also comprise an oil-in-water ammonium cations include alkyl ammonium cations such as emulsion system having complex structures such as liquid monoalkyl, dialkyl, trialkyl, and tetraalkyl ammonium cat crystals and crystalline gel networks. The nature of liquid ions wherein the alkyl groups are independently selected crystals, the formation of liquid crystals, and the properties from straight and branched chain alkyl groups having from and the advantages of liquid crystals are described further in about 1 to about 30 carbon atoms. Other examples of G. Dahms, Properties of O/W Emulsions With Anisotropic Substituted ammonium cations include alkanol ammonium 10 Lameliar Phases, 101 Cosmetics de Toiletries, 113-115 cations such as monoalkanol, dialkanol, trialkanol, and (1986); P. Loll, Liquid Crystals in Cosmetic Emulsions, ICI tetraalkanol ammonium cations wherein the alkanol groups Surfactants' Publication RP94-93E; and G. M. Eccleston, are independently selected from straight and branched chain Multiple-Phase Oil-In-Water Emulsions, 41, J. Soc. Cosmet. alkanol groups having from about 2 to about 30 carbon Chem., 1-22, (January/February 1990); all of which are atoms. Nonlimiting examples of substituted alkyl ammo 5 incorporated herein by reference in their entirety. nium and alkanol ammonium cations include methyl ammo The exact level of the topical carrier employed will vary nium, ethyl ammonium, dimethyl ammonium, diethyl depending upon the carrier chosen, the levels of the essential ammonium, trimethyl ammonium, triethyl ammonium, tet components, and the levels of any optional components. The ramethyl ammonium, tetraethyl ammonium, dimethyl dis topical carrier comprises from about 50% to about 99.875%, tearyl ammonium, monoethanol ammonium, diethanol preferably from about 70% to about 99%, and most prefer ammonium, triethanol ammonium, tetraethanol ammonium, ably from about 75% to about 96%, of the compositions of monoethanoltrimethyl ammonium cations, and mixtures the present invention. thereof. pH Of The Compositions Among the metabisulfite, sulfite, and hydrogen sulfite Without being limited by theory, it is believed that pH can salts useful herein, the metabisulfite salts are preferred. 25 be a factor contributing to the chemical and physical stabil Preferred metabisulfite salts include those selected from the ity of a composition containing dihydroxyacetone. For group consisting of sodium metabisulfite (i.e. Na2S2O3), example, it is well known that dihydroxyacetone rapidly potassium metabisulfite (i.e. K2S2O3), ammonium met degrades at extremes of pH, and that at such extremes both abisulfite (i.e. (NH)2(SO4)), and mixtures thereof. Most the physical and chemical stability of the compositions can preferred is sodium metabisulfite. 30 be adversely effected. Topical Carrier Although the compositions of the present invention can The compositions of the present invention comprise as an encompass a wide range of pH values, the compositions essential component atopical carrier or diluent which can be preferably have a pH from about 2.5 to about 7, more of a wide variety of different forms. The term “topical preferably from about 2.5 to about 6, and most preferably carrier' means a vehicle or base composition for containing, 35 from about 3.5 to about 5. The pH will depend upon the delivering, or carrying the essential components and any combination of essential and optional ingredients chosen. additional or optional components of the present invention An acidic buffer system can be useful, but is not required, in to the surface of the skin. The topical carrier should be one helping to maintain the desired pH of the compositions. that is pharmaceutically acceptable because of its intended Nonlimiting examples of acidic buffer systems useful herein use on human skin. The topical carrier can contain a wide 40 include those selected from the group consisting of citrate, variety of common pharmaceutical and cosmetic ingredients acetate, phosphate, and benzoate buffers. typically used in the beauty care industry, nonlimiting It is well known to one of ordinary skill in the art that the examples of which are described below. The topical carrier pH of an aqueous system is readily measured utilizing pH can be in the form of an emulsion including, but not limited meters and commercially available indicator papers. In the to, oil-in-water, water-in-oil, water-in-oil-in-water, water-in 45 case of aqueous systems the pH value is readily made on the silicone and oil-in-water-in-silicone emulsions. These emul aqueous phase. In the case of primarily non-aqueous sys sions can cover a broad range of consistencies including thin tems, e.g. in emulsion systems having a continuous oil phase lotions (which can also be suitable for aerosol or nonaerosol (i.e. water-in-oil emulsions) the pH value would correspond spray delivery), creamy lotions, light creams, heavy creams, to the internal water phase of such systems. and the like. The topical carrier can also comprise an 50 Additional Components aqueous-based system containing other water-soluble sol The compositions of the present invention can comprise a vents such as alcohols. These aqueous-based systems can be wide range of additional components. These additional formulated over a wide range of viscosities and can be components can comprise the topical carrier or can comprise thickened with a wide variety of water-compatible thicken components which are delivered from the topical carrier. ing agents to form viscous liquids and gels. The lower 55 The CTFA Cosmetic Ingredient Handbook, Second Edi viscosity aqueous-based systems can also be delivered as tion, 1992, which is incorporated by reference herein in its aerosol and nonaerosol sprays. The viscosity of the compo entirety, describes a wide variety of nonlimiting cosmetic sitions herein will therefore vary depending upon the exact and pharmaceutical ingredients commonly used in the ingredients chosen and the type of carrier desired. For beauty care industry, which are suitable for use in the example, the viscosity of the compositions herein can range 60 compositions of the present invention. Nonlimiting from about 0.1 cps to about 5,000,000 cps, or more. Non examples of functional classes of these ingredients are limiting examples of topical carriers useful in the present described at page 537 of this reference. Examples of these invention are described in the following four references all functional classes include: abrasives, absorbents, antiacne of which are incorporated herein by reference in their agents, anticalking agents, antifoaming agents, antimicrobial entirety: "Sun Products Formulary' Cosmetics & Toiletries, 65 agents, antioxidants, binders, biological additives, buffering vol. 105, pp. 122-139 (December 1990); "Sun Products agents, bulking agents, chelating agents, chemical additives, Formulary”, Cosmetics & Toiletries, vol. 102, pp. 117-136 colorants, cosmetic astringents, cosmetic biocides, denatur 5,514,437 7 8 ants, drug astringents, emulsion stabilizers, external analge and their salts as well as inorganic particulate materials. sics, film formers, fragrance components, humectants, Without being limited by theory, it is believed that sunscreen opacifying agents, pH adjusters, preservatives, propellants, agents provide protection from ultraviolet radiation by one reducing agents, skin bleaching agents, skin-conditioning or more of the following mechanisms including absorption, agents (emollients, humectants, miscellaneous, and occlu scattering, and reflection of the ultraviolet radiation. Non sive), skin protectants, solvents, sunscreen agents, surfac limiting examples of these sunscreen agents are described in tants (cleansing agents, emulsifying agents, foam boosters, hydrotropes, solubilizing agents, suspending agents, and U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11, nonsurfactants), ultraviolet light absorbers, viscosity 1992; U.S. Pat. No. 5,073,372, to Turner et al., issued Dec. decreasing agent, and viscosity increasing agents (aqueous 17, 1991; U.S. Pat. No. 5,073,371, to Turner et al. issued and nonaqueous). O Dec. 17, 1991; U.S. Pat. No. 5,160,731, to Sabatelli et al., Some nonlimiting examples of these additional compo issued Nov. 3, 1992; U.S. Pat. No. 5,138,089, to Sabatelli, nents cited in the CTFA Cosmetic Ingredient Handbook, as issued Aug. 11, 1992; U.S. Pat. No. 5,041,282, to Sabatelli, well as other materials useful herein, include the following: issued Aug. 20, 1991; U.S. Pat. No. 4,999,186, to Sabatelli vitamins and derivatives thereof (e.gtocopherol, tocopherol et al., issued Mar. 12, 1991; U.S. Pat. No. 4,937,370, to acetate, retinoic acid, retinol, retinoids, and the like); thick 15 Sabatelli, issued Jun. 26, 1990; and Segarin, et al., at Chapter ening agents; crosslinked acrylic acid homopolymers avail VIII, pages 189 et seq., of Cosmetics Science and Technol able as the carbomers from B.F. Goodrich; acrylates/C10-30 ogy; all of these documents being incorporated herein by alkyl acrylate crosspolymers available as Carbopol 1342 reference in their entirety. Preferred among the sunscreen from B.F. Goodrich; gums, waxes (both naturally occurring agents are those selected from the group consisting of and synthetic); polymers for aiding the film-forming prop 20 2-ethylhexyl p-methoxycinnamate, octyl salicylate, octoc erties and substantivity of the composition (such as a rylene, oxybenzone, 2-ethylhexyl N,N-dimethylaminoben copolymer of eicosene and vinyl pyrrolidone, an example of zoate, paminobenzoic acid, 2-phenyl-benzimidazole-5-sul which is available from GAF Chemical Corporation as fonic acid, homomenthyl salicylate, DEA Ganex V-220"); preservatives for maintaining the antimi p-methoxycinnamate, 4,4' methoxy-t-butyldibenzoyl crobial integrity of the compositions; skin penetration aids 25 methane, 4-isopropylidibenzoylmethane, 3-(4-methylben such as DMSO, 1-dodecylazacycloheptan-2-one (available Zylidene) camphor, 3-benzylidene camphor, 4-N,N-dim as Azone from the Upjohn Co.) and the like; anti-acne ethylaminobenzoic acid ester with 2,4- medicaments (e.g., resorcinol, salicylic acid, erythromycin, dihydroxybenzophenone, 4-N,N-dimethylaminobenzoic benzoyl peroxide, zinc, and the like); skin bleaching (or acid ester with 2-hydroxy-4-(2hydroxyethoxy)benzophe lightening) agents including but not limited to hydro 30 none, 4-N,N-dimethylaminobenzoic acid ester with 4-hy quinone, kojic acid; antioxidants; chelators and sequestrants; droxydibenzoyl-methane, 4-N,N-dimethylaminobenzoic and aesthetic components such as fragrances, pigments, acid ester with 4-(2-hydroxyethoxy)dibenzoylmethane, 4-N, colorings, essential oils, skin sensates, astringents, skin N-di(2-ethylhexyl)aminobenzoic acid ester with 2,4-dihy soothing agents, skin healing agents and the like, nonlimit droxybenzophenone, 4-N,N-di(2ethylhexyl)aminobenzoic ing examples of these aesthetic components include pan 35 acid ester with 2-hydroxy-4-(2hydroxyethoxy)benzophe thenol and derivatives (e.g. ethyl panthenol), aloe vera, none, 4-N,N-di(2-ethylhexyl)aminobenzoic acid ester with pantothenic acid and its derivatives, clove oil, menthol, 4-hydroxydibenzoylmethane, 4-N,N- camphor, eucalyptus oil, eugenol, menthyl lactate, witch di(2ethylhexyl)aminobenzoic acid ester with 4-(2-hydroxy hazel distillate, allantoin, bisabolol, dipotassium glycyrrhiz ethoxy)dibenzoylmethane, 4-N,N-(2-ethylhexyl)methy inate and the like; and skin conditioning agents such as the 40 laminobenzoic acid ester with 2,4-dihydroxybenzophenone, propoxylated glycerols described in U.S. Pat. No. 4,976,953, 4-N,N-(2ethylhexyl)methylaminobenzoic acid ester with to Orr et al., issued Dec. 11, 1990, which is incorporated by 2-hydroxy-4-(2hydroxyethoxy)benzophenone, 4-N,N-(2- reference herein in its entirety. Especially preferred optional ethylhexyl)methylaminobenzoic acid ester with 4-hydroxy ingredients include Sunscreen agents and amino acids as dibenzoylmethane, 4-N,N-(2-ethylhexyl)methylaminoben further described below. 45 zoic acid ester with 4-(2-hydroxyethoxy)dibenzoylmethane, Sunscreen Agents titanium dioxide, zinc oxide, iron oxide, and mixtures The compositions of the present invention can comprise thereof. one or more sunscreen agents. When a sunscreen agent is More preferred for use in the compositions described employed, it is found that the compositions of the present herein are the sunscreen agents selected from the group invention are also useful for protecting human skin from the 50 consisting of 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, harmful effects of ultraviolet radiation. 2-ethylhexyl p-methoxycinnamate, octocrylene, octyl sali The sunscreen agent can comprise from about 0.1% to cylate, homomenthyl salicylate, p-aminobenzoic acid, oxy about 30%, more preferably from about 0.5% to about 25%, benzone, 2-phenylbenzimidazole-5-sulfonic acid, DEA and most preferably from about 1% to about 20% of the pmethoxycinnamate, 4,4' -methoxy-t-butylidibenzoyl compositions of the present invention. Exact amounts of 55 methane, 4-isopropyl dibenzoylmethane, 3-(4-methylben Sunscreen agent will vary depending upon the sunscreen or Zylidene) camphor, 3-benzylidene camphor, 4-N,N-(2-eth sunscreens chosen and the desired Sun Protection Factor ylhexyl)methylaminobenzoic acid eSite with (SPF) to be achieved. SPF is a commonly used measure of 4-(2hydroxyethoxy)dibenzoylmethane, titanium dioxide, photoprotection of a sunscreen against erythema. The SPF is Zinc oxide, iron oxide, and mixtures thereof. defined as the ratio of the ultraviolet energy required to 60 Most preferred for use in the compositions described produce minimal erythema on protected skin to that required herein are the sunscreen agents selected from the group to produce the same minimal erythema on unprotected skin consisting of 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, in the same individual. See Federal Register, Vol. 43, No. 2-ethylhexyl p-methoxycinnamate, octocrylene, octyl sali 166, pp. 38206-38269, Aug. 25, 1978, which is incorporated cylate, oxybenzone, 2-phenylbenzimidazole-5-sulfonic herein by reference in its entirety. 65 acid, 4,4'-methoxy-t-buyldibenzoylmethane, 3-(4-methyl A wide variety of sunscreen agents are useful herein. benzylidene) camphor, 3-benzylidene camphor, 4-N,N- These sunscreen agents include both organic compounds (2ethylhexyl)methylaminobenzoic acid ester with 4-(2-hy 5,514,437 9 10 droxyethoxy)dibenzoylmethane, titanium dixoide, Zinc entirety. Lysine is a compound having a chiral center at the oxide, iron oxide, and mixtures thereof. two carbon position and can therefore exist in either the (R) Amino Acids and Pharmaceutically Acceptable Salts or (S) enationeric form. Traditionally, amino acid stere The compositions of the present invention can also com ochemistry is also defined in terms of D and L configura prise an amino acid, or a pharmaceutically acceptable salt 5 tions, as is commonly done for carbohydrates. The naturally thereof selected from the group consisting of alanine, valine, occurring form of lysine is the Lenantiomer, which corre leucine, isoleucine, proline, methionine, phertylalanine, sponds to the (S) configuration. The lysine molecule can tryptophan, glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, lysine, arginine, histidine, and mix form salts at its carboxylic acid group with cationic species tures thereof. These amino acids or their pharamaceutically and at either one or both of its amino groups with anionic acceptable salts comprise from about 0.1% to about 10%, 10 species. Because the lysine molecule contains a carboxylic more preferably from about 0.25% to about 5%, and most acid group and two amino groups, the molecule therefore preferably from about 0.50% to about 1.5% of the compo exhibits three pK values at 2.16, 9.20, and 10.80. It is sitions herein. believed that these pK values correspond to the carboxylic Amino acids and their pharmaceutically acceptable salts acid group, the amino group at the two carbon position, and described herein are useful for modifying the artificial tan 5 the amino group at the six carbon position, respectively. The color obtained on human skin using dihydroxyacetone. pH of the medium in which the lysine is present will Dihydroxyacetone is known to react with various nitrogen therefore determine whether any of these sites will be in containing compounds to produce a brown or tan color. See, their neutral or ionic form. See A. Streitwieser, Jr. and C. H. e.g. Kawashima et al., “Nonenzymatic Browning Reactions Heathcock, Introduction to Organic Chemistry, Chapter 28, of Dihydroxyacetone With Amino Acids or Their Esters', pp., 814–860, Macmillan Pub. Co., Inc., N.Y., 1976, which Agric. Biol. Chem. 44(7), 1595–1599 (1980), and M. F. is incorporated herein by reference in its entirety. Bobin et al., “Effects of Color Adjuvants On the Tanning As described above, most preferred among the amino Effect of Dihydroxyacetone', J. Soc. Cosmet. Chem., 35 acids are lysine and its pharmaceutically acceptable salts. 265-272 (August 1984), both of which are incorporated by Nonlimiting examples of pharmaceutically acceptable lysine reference herein in their entirety. However, this reaction, has 25 salts include lysine sodium salt, lysine potassium salt, lysine previously been difficult to control and has been an obstacle calcium salt, lysine magnesium salt, lysine hydrochloride, to formulating a stable artificial tanning composition (i.e. lysine dihydrochloride, lysine succinate, lysine phosphate, especially one that is resistant to developing off-odors and lysine hydrogen sulfate, lysine di(hydrogen sulfate), lysine discoloration) containing both dihydroxyacetone and an carbonate, lysine hydrogen carbonate, lysine di(hydrogen amino acid or a salt thereof. A possible solution to this carbonate), and mixtures thereof. It is found that among incompatibility problem is to formulate the dihydroxyac these salts that lysine hydrochloride and lysine dihydrochlo etone separately from the amino acid and to either deliver ride are preferred. the formulations sequentially from separate containers or Methods for Providing an Artificial Tan and for Protecting simultaneously from a dual-chambered dispensing device. the Skin from UV Radiation However, these alternatives are inconvenient, cumbersome, 35 The compositions of the present invention are useful for and expensive. See, e.g. European Patent No. 527,864, providing an artificial tan to human skin. These composi assigned to Unilever, published Jun. 23, 1993. In the stabi tions, when optionally formulated to contain sunscreen lized compositions of the present invention, it is found that compounds as described above, are also useful for protect the amino acids or their pharmaceutically acceptable salts ing human skin from the harmful effects of ultraviolet can be formulated without the incompatibility problems 40 radiation. To obtain an artificial tan and/or protection from previously encountered. the harmful effects of UV radiation, an effective amount of As described above, the amino acids or their pharmaceu the composition of the present invention is applied to the tically acceptable salts thereof useful herein are those skin. The term "effective' means an amount of the present selected from the group consisting of alanine, valine, leu composition to provide an artificial tan and/or protection cine, isoleucine, proline, methionine, phenylalanine, tryp 45 from ultraviolet radiation, but not so much as to cause any tophan, glycine, serine, threonine, cysteine, tyrosine, aspar undesirable side effects or skin reactions. The term “protec agine, glutamine, lysine, arginine, histidine, and mixtures tion' means that the present compositions attenuate or thereof. Preferred are those selected from the group consist reduce the amount of ultraviolet radiation reaching the ing of lysine, arginine, histidine, and mixtures thereof. Most skin's surface thereby reducing the incidence of undesirable preferred is the amino acid lysine and its pharmaceutically 50 skin reactions such as sunburn, erythema, skin cancer, and acceptable Salts. photoinduced skin aging. As described above, one com Lysine, or a pharmaceutically acceptable salt thereof, is monly used measure of a compositions effectiveness against most preferred for use herein, because of the especially ultraviolet radiation is the SPF factor. natural looking and rapidly developing artificial tan obtained A wide range of quantities of the compositions of the from the addition of this material to a dihydroxyacetone 55 present invention can be employed to provide an artificial containing composition. Lysine is one of the commonly tan and/or protection from the harmful effects of ultraviolet occurring amino acids and is also known as 2,6diaminohex radiation. Quantities of the present compositions which are anoic acid. Lysine contains two amino groups and a single typically applied to provide an artificial tan and/or protection carboxylic acid group and can be represented by the chemi from the harmful effects of ultraviolet radiation typically cal formula CHNO and the following chemical struc 60 range from about 0.1 m/cm' to about 10 mg/cm'. A par tre. ticularly useful amount to use is about 2 mg/cm.

EXAMPLES 65 The following examples further describe and demonstrate See The Merck Index, Tenth Edition, Entry 5453, page 806 embodiments within the scope of the present invention. The (1983), which is incorporated herein by reference in its examples are given solely for the purpose of illustration and 5,514,437 11 12 are not to be construed as limitations of the present inven EXAMPLES IV-V. tion, as many variations thereof are possible without depart ing from the spirit and scope of the invention. Artificial Tanning Creams Containing Sunscreens An oil-in-water emulsion is prepared by combining the Ingredients are identified by chemical or CTFA name. following ingredients using conventional mixing tech EXAMPLES I-III niques. Examples IV, V, and VI correspond to light, medium, Artificial Tanning Creams and dark artificial tanning creams, respectively. An oil-in-water emulsion is prepared by combining the following ingredients using conventional mixing tech Examples IV W WE niques. Examples I, II, and III correspond to light, medium, 10 Ingredients Weight Percent and dark artificial tanning creams, respectively. PHASEA Water qs 100 qs 100 qs 100 Examples I II. III Glycerin 5.00 5.00 5.00 Ingredients Weight Percent 15 Magenisum Aluminum Silicate 0.50 0.50 0.50 Xanthan Gum 0.30 0.30 0.30 PHASEA Disodium EDTA 0.10 0.10 0.10 Water qs 100 qs 100 qs 100 PHASEB Glycerin 5.00 5.00 5.00 2-Ethylhexyl p-Methoxycinnamate 2.00 2.00 2.00 Magenisum Aluminum Silicate 0.50 0.50 0.50 20 Cyclomethicone 3.00 3.00 3.00 Xanthan Gum 0.30 0.30 0.30 Cetyl Alcohol 2.00 2.00 2.00 Disodium EDTA 0.10 0.10 0.10 Stearyl Alcohol 2.00 2.00 2.00 PHASEB Steareth-20 1.00 1.00 00 Octocrylene 100 0.00 0.00 Cyclomethicone 3.00 3.00 3.00 Oxybenzone 1.00 0.00 0.00 Cetyl Alcohol 2.00 2.00 2.00 Polysorbate 60 0.50 0.50 0.50 Stearyl Alcohol 2.00 2.00 2.00 25 Dimethicone Copolyol 0.50 0.50 0.50 Steareth-20 1.00 1.00 00 Glyceryl Stearate (and) 0.25 0.25 0.25 Polysorbate 60 0.50 0.50 0.50 PEG-100 Stearate Dimethicone Copolyol 0.50 0.50 0.50 PHASEC Glyceryl Stearate (and) 0.25 0.25 0.25 PEG-100 Stearate Water 8.00 9.00 110 PHASEC 30 Dihydroxyacetone 4.00 5.00 6.00 Sodium Metabisulfite 0.25 0.25 0.25 Water 8.00 9.00 10 Phase D Dihydroxyacetone 4.00 5.00 6.00 Sodium Metabisulfite 0.25 0.25 0.25 Water 2.50 2.50 2.50 Phase D Butylene Glycol 2.50 2.50 2.50 35 DMDM Hydantoin (and) 0.25 0.25 O.25 Water 2.50 2.50 2.50 Iodopropynyl Butyl Butylene Glycol 2.50 2.50 2.50 carbamate DMDM Hydantoin (and) 0.25 0.25 0.25 Sorbic Acid 0.10 0.10 0.10 Iodopropynyl Butyl PHASEE carbamate Sorbic Acid 0.10 0.10 0.10 Fragrance 0.15 0.15 0.5 PHASEE 40 Fragrance 0.15 0.15 0.15 In a suitable vessel the Phase A ingredients are dispersed in the water with stirring and heated to 70-75° C. In a In a suitable vessel the Phase A ingredients are dispersed separate vessel the Phase B ingredients are combined and in the water with stirring and heated to 70°-75° C. In a 45 heated to 70-75° C. and maintained until all ingredients are separate vessel the Phase B ingredients are combined and melted. Phase B is slowly added to Phase A and the resulting heated to 70-75° C. and maintained until all ingredients are emulsion is stirred for 15 minutes while maintaining a melted. Phase B is slowly added to Phase A and the resulting temperature of 70-75° C. The emulsion is then allowed to emulsion is stirred for 15 minutes while maintaining a cool to 40°C. In a separate vessel the ingredients of Phase temperature of 70-75° C. The emulsion is then allowed to 50 Care added and stirred until dissolved. When the emulsion cool to 40°C. In a separate vessel the ingredients of Phase is at or below 40°C, Phase C is added. In a separate vessel Care added and stirred until dissolved. When the emulsion the ingredients of Phase D are added, stirred and warmed to is at or below 40°C., Phase C is added. In a separate vessel 40 C. until all are dissolved. Phase D is next added and the ingredients of Phase D are added, stirred and warmed to stirring is continued for 15 minutes. When the emulsion is at 40° C. until all are dissolved. Phase D is next added and 55 35° C., Phase E is added and stirring is continued for 5 stirring is continued for 15 minutes. When the emulsion is at minutes followed by cooling to room temperature. 35° C., Phase E is added, and stirring is continued until The resulting sunless tanning creams exhibit good physi cooled to room temperature. cal and chemical stability and are useful for topical appli The resulting sunless tanning creams exhibit good physi cation to human skin to provide an artificial tan and to cal and chemical stability and are useful for topical appli 60 provide protection from the harmful effects of ultraviolet cation to human skin to provide an artificial tan. radiation. In variations on these formulas the sodium metabisulfite In variations on these formulas the sodium metabisulfite level is varied over the range from about 0.025% to about level is varied over the range from about 0.025% to about 5%. In further variations, the sodium metabisulfite is 5%. In further variations, the sodium metabisulfite is replaced with an equal weight of sodium sulfite, sodium 65 replaced with an equal weight of sodium sulfite, sodium bisulfite, potassium metabisulfite, or ammonium met bisulfite, potassium metabisulfite, or ammonium met abisulfite. abisulfite. 5,514,437 13 14 EXAMPLES VII-VIII EXAMPLE IX ARTIFICIAL TANNING GEL Artificial Tanning Creams An artificial tanning gel is prepared utilizing conventional An oil-in-water emulsion is prepared by combining the mixing techniques. following ingredients using conventional mixing tech 5 niques. Examples VII and VIII correspond to non-sunscreen Ingredients Weight Percent and sunscreen-containing formulas respectively. Water qs Dihydroxyacetone 3.00 10 Glycerin 3.00 Examples VII VIII Polysorbate 20 1.00 Ingredients Weight Percent Triethanolamine 0.50 Carbomer 940 0.40 Phase A DMDM Hydantoin 0.10 Water qs 100 qs 100 IsopropylC12-15 Pareth-9 0.10 Cetyl Hydroxyethylcellulose 0.50 0.50 15 Carboxylate Disodium EDTA 0.030 0.03 Diazolidinyl Urea 0.10 Disodium EDTA 0.05 Phase B Fragrance 0.30 PPG-15 Stearyl Ether 11.0 0 Sodium Metabisulfite 0.25 2-Ethylhexyl p-Methoxycinnamate O 2.00 Oxybenzone 0 1.00 20 Octocrylene O 1.00 In a suitable vessel, all ingredients except the triethano Dimethicone & 2.00 2.00 lamine and 1% of the water are combined with stirring. The Trimethylsiloxysilicate triethanolamine and remaining 1% water are combined in a Dimethicone 1.00 1.00 separate vessel, and then slowly added to the rest of the Glyceryl Stearate 2.60 2.60 PVP/Eicosene Copolymer 0.80 0.80 25 mixture while stirring is continued. Cetyl Alcohol 0.75 0.75 The resulting artificial tanning gel has improved stability Stearyl Alcohol 0.50 0.50 and is useful for topical application to the skin to provide an Ceteareth-12 0.50 0.50 artificial tan. Ceteareth-20 0.50 0.50 In variations on these formulas the sodium metabisulfite Phase C 30 level is varied over the range from about 0.025% to about Water 2.00 2.00 5%. In further variations, the sodium metabisulfite is Butylene Glycol 2.00 2.00 replaced with an equal weight of sodium sulfite, sodium DMDM Hydantoin (and) 0.20 0.20 Iodopropynyl Butylcarbamate bisulfite, potassium metabisulfite, or ammonium met Phase D abisulfite. 35 Water 6.00 6.00 Dihydroxyacetone 3.00 3.00 EXAMPLE X Sodium Metabisulfite 0.25 0.25 Phase E ARTIFICIALTANNING SPRAY An artificial tanning spray is prepared utilizing conven Fragrance 1.00 1.00 40 tional mixing techniques.

In a suitable vessel the Phase A ingredients are dispersed Ingredients Weight Percent in the water and heated to 75°–85°C. In a separate vessel the Water qs 100 Phase B ingredients are combined and heated to 85°-90° C. Dihydroxyacetone 3.00 45 Sodium Metabisulfite 0.25 until melted and this mixture is then added to Phase A to Dimethylisosorbide 3.00 form the emulsion. The emulsion is cooled to 40-45° C. Glycereth-7 Triaceate 1.00 PEG-15 Laurate 0.50 with continued mixing. In a separate vessel, the Phase C Propylene Glycol 1.00 Methylparaben 0.10 ingredients are combined and the resulting solution is mixed 50 Propylparaben 0.0 into the emulsion. In a separate vessel, the dihydroxyacetone Glycerin 3.00 is dissolved in water to form Phase D, and the resulting Polysorbate 20 100 solution is mixed into the emulsion. Finally, the fragrance, In a suitable vessel, all ingredients are combined and Phase E, is added to the emulsion with mixing, which is then 55 mixed until uniform. cooled to 30°-35°C., and then to room temperature. The resulting artificial tanning spray has improved sta These emulsions have improved stability and are useful bility and can be packaged in either a conventional non aersol pump spray bottle or can be combined with conven for topical application to the skin to provide an artificial tan tional propellant ingredients and packaged in an aerosol and/or protection from ultraviolet radiation. 60 canister for topical application to the skin to provide an In variations on these formulas the sodium metabisulfite artificial tan. level is varied over the range from about 0.025% to about In variations on these formulas the sodium metabisulfite 5%. In further variations, the sodium metabisulfite is level is varied over the range from about 0.025% to about 5%. In further variations, the sodium metabisulfite is replaced with an equal weight of sodium sulfite, sodium 65 replaced with an equal weight of sodium sulfite, sodium bisulfite, potassium metabisulfite, or ammonium met bisulfite, potassium metabisulfite, or ammonium met abisulfite. abisulfite. 5,514,437 15 16 EXAMPLES XI-XIII (a) from about 0.1% to about 20% dihydroxyacetone, Artificial Tanning GelNetwork Emulsions Containing Dihy (b) from about 0.025% to about 5% of a salt selected from droxyacetone and Lysine Hydrochloride the group consisting of metabisulfite salts, sulfite salts, An oil-in-water emulsion is prepared by combining the hydrogen sulfite salts, and mixtures thereof, and following ingredients using conventional mixing tech 5 (c) a topical carrier. niques. Examples XI, XII, and XIII correspond to light, 2. A composition according to claim 1 wherein said medium, and dark artificial tanning creams, respectively. metabisulfite, sulfite, and hydrogen sulfite salts are selected from the group consisting of alkali metal salts, alkaline metal salts, ammonium salts, and mixtures thereof. Examples XI XI XII 10 Ingredients Weight Percent 3. A composition according to claim 1 wherein said metabisulfite, sulfite, and hydrogen sulfite salts are selected PHASEA from the group consisting of sodium salts, potassium salts, Water qs 100 qs 100 qs 100 ammonium salts, and mixtures thereof. Glycerin 5.00 5.00 5.00 15 4. A composition according to claim 1 wherein said salt is Cetyl Hydroxyethylcellulose 0.15 0.15 0.15 a metabisulfite salt. Disodium EDTA 0.10 0.10 0.10 Xanthan Gum 0.0 0.10 0.10 5. A composition according to claim 4 wherein said PHASEB metabisulfite salt is selected from the group consisting of alkali metal metabisulfite salts, alkaline metal metabisulfilte Cetyl Alcohol 2.13 2.13 2.13 Behenyl Alcohol 2.13 2.3 2.13 20 salts, ammonium metabisulfite salts, and mixtures thereof. sohexadecane 1.00 00 1.00 6. A composition according to claim 5 wherein said PPG-3 Myristyl Ether 1.00 1.00 1.00 metabisulfite salt is selected from the group consisting of Cyclomethicone D5 100 1.00 1.00 Ceteareth-20 0.45 0.45 O.45 Sodium metabisulfite, potassium metabisulfite, ammonium Ceteareth-12 0.30 0.30 0.30 metabisulfite, and mixtures thereof. PHASEC 25 7. A composition according to claim 6 wherein said metabisulfite salt is sodium metabisulfite. Water 9.00 10.00 2.00 Dihydroxyacetone 3.30 4.30 5.30 8. A composition according to claim 4 comprising from Butylene Glycol 2.50 2.50 2.50 about 0.05% to about 5% of said metabisulfite salt. L-Lysine Hydrochloride 0.75 0.75 0.75 DMDM Hydantoin (and) O.25 0.25 0.25 9. A composition according to claim 4 comprising from Iodopropynyl Butylcarbamate 30 about 0.05% to about 1% of said metabisulfite salt. Sodium Metabisulfite 0.25 0.35 0.45 10. A composition according to claim 4 comprising from PHASED about 0.1% to about 1% of said metabisulfite salt. Fragrance 0.15 0.15 0.15 11. A composition according to claim 4 comprising about 0.25% of said metabisulfite salt. 35 In a suitable vessel the Phase A ingredients are dispersed 12. A composition according to claim 11 comprising from in the water with stirring and heated to 70°-75° C. In a about 2% to about 7% dihydroxyacetone. separate vessel the Phase B ingredients are combined and 13. A composition according to claim 11 comprising from heated to 70-75° C. and maintained until all ingredients are about 3% to about 6% dihydroxyacetone. melted. Phase B is slowly added to Phase A and the resulting 40 14. A composition according to claim 1 wherein said emulsion is homogenized for 15 minutes while maintaining composition further comprises from about 0.5% to about a temperature of 70-75° C. The emulsion is then allowed 20% of a sunscreen selected from the group consisting of to cool to 40°C. In a separate vessel the ingredients of Phase 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, 2-ethylhexyl C are added and stirred until all are dissolved. Phase C is p-methoxycinnamate, octocrylene, octyl salicylate, oxyben next added and the emulsion is stirred for 15 minutes. When 45 Zone, 2-phenylbenzimidazole-5-sulfonic acid, 4,4'-meth the emulsion is at 35° C., Phase D is added and stirring is oxy-t-buyldibenzoylmethane, 3-(4-methylbenzylidene) continued until to cooled to room temperature. camphor, 3-benzylidene camphor, 4-N,N-(2-ethylhexyl)m- The resulting compositions exhibit good physical and ethylaminobenzoic acid ester with 4-(2-hydroxyethoxy chemical stability, improved color development character )dibenzoylmethane, titanium dioxide, zinc oxide, iron oxide, istics, and are useful for topical application to human skin to 50 provide an artificial tan. and mixtures thereof. In variations on these formulas the sodium metabisulfite 15. A composition according to claim 1 wherein said level is varied over the range from about 0.025% to about composition further comprises from about 0.1% to about 5%. In further variations, the sodium metabisulfite is 10% of an amino acid or pharmaceutically acceptable salt replaced with an equal weight of sodium sulfite, sodium 55 thereof selected from the group consisting of alanine, valine, bisulfite, potassium metabisulfite, or ammonium met leucine, isoleucine, proline, methionine, phenylalanine, abisulfite. tryptophan, glycine, serine, threonine, cysteine, tyrosine, In further variations on these formulas the L-lysine hydro asparagine, glutamine, lysine, arginine, histidine, and mix chloride is varied over the range from about 0.5% to about tures thereof. 1.5% by weight of the total composition. In further varia 50 tions, the L-lysine hydrochloride is replaced with an equiva 16. A composition according to claim 1 wherein said lent weight of L-lysine or L-lysine dihydrochloride or other composition further comprises from about 0.1% to about amino acids or their pharmaceutically acceptable salts such 10% of an amino acid or a pharmaceutically acceptable salt as arginine and histidine. thereof selected from the group consisting of lysine, argin What is claimed is: 65 ine, histidine, and mixtures thereof. 1. An artificial tanning composition having improved 17. A composition according to claim 1 wherein said stability comprising: composition further comprises from about 0.1% to about 5,514,437 17 18 10% of an amino acid or a pharmaceutically accetable salt 19. A method for providing an artificial tan to human skin thereof selected from the group consisting of L-lysine, and protecting human skin from the harmful effects of L-lysine hydrochloride, L-lysine dihydrochloride, and mix ultraviolet radiation comprising topically applying to the tures thereof. skin an effective amount of a composition according to claim 18. A method for providing an artificial tan to human skin 14. topically applying to the skin an effective amount of a composition according to claim 1. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 5,514,437 Page 1 of 2 DATED May 7, 1996 INVENTOR(S) Paul R. Tanner et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

At column 4, lines 31-32"XP (S.O.),” should read-X(S.O.)--. At column 4, line 32 “XP (SO)," should read-X(SO,)--. At column 4, line 33 "XP.(HSO)," should read-X".(HSO).--. At column 6, line 10 "Lameliar' should read --Lamellar--. At column 7, line 10"agent” should read-agents--. At column 8, line 22 "paminobenzoic' should read -p-aminobenzoic-. At column 8, line 25 "3-(4-methylbenzylidene)” should read -3-(4-methylbenzylidene)--. At column 8, line 29"2-hydroxy-4-(2hydroxyethoxy)” should read --2-hydroxy-4-(2-hydroxyethoxy)--. At column 8, line 34"4-N,N-di(2ethylhexyl)' should read --4-N,N-di(2-ethylhexyl)--. At column 8, line 35 “2-hydroxy-4-(2hydroxyethoxy)" should read -2-hydroxy-4-(2-hydroxyethoxy)--. At column 8, lines 37-38"4-N,N-di(2ethylhexyl)" should read --4-N,N-di(2-ethylhexyl)--. At column 8, line 41 “4-N,N-(2ethylhexyl)” should read --4-N,N-(2-ethylhexyl)--. At column 8, line 42"2-hydroxy-4-(2hydroxyethoxy)' should read -2-hydroxy-4-(2-hydroxyethoxy)--. At column 8, line 54"pmethoxycinnamate' should read -p-methoxycinnamate--. At column 8, line 58"4-(2hydroxyethoxy)' should read -4-(2-hydroxyethoxy)--. At column 8, lines 65-66 “3-(4-methylbenzylidene)” should read -3-(4-methylbenzylidene)--. At column 8, lines 66-67 "4-N,N-(2ethylhexyl)' should read --4-N,N-(2-ethylhexyl)--.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. 5,514,437 Page 2 of 2 DATED : May 7, 1996

INVENTOR(S) : Paul R. Tanner et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

At column 9, line 7 "phertylalanine' should read -phenylalanine--. At column 9, line 57 "2,6diaminohexanoic' should read --2,6-diaminohexanoic--. At column 10, line 60 "0.1 m/cm” should read -0.1 mg/cm--.

Signed and Sealed this

Ninth Day of March, 1999

Q. ToDD DICKINSON Attesting Officer Acting Commissioner of Patents and Tradencirks